Detergent compositions

ABSTRACT

The invention describes the use of salts of sulphonated fatty acids as detergency builders. The use of C14 to C20 acids is required and a formulation containing 10 to 75% of a builder component including at least one sulphonated fatty acid salt and 5 to 50% of a detergent active is proposed. Preferred actives, which demonstrate increased detergency at specific ratios, are alkylaryl sulphonates, nonionic materials and alkane sulphonates.

United States Patent Davies et al.

DETERGENT COMPOSITIONS Inventors: James Francis Davies, Wirral;

Charles Rowland Gauterin, Farndon; David Wynn Lewis Griffiths;Christopher Charles Storer, both of Wirral, all of England Assignee:Lever Brothers Company, New

York, N.Y.

Filed: Dec. 27, 1973 Appl. No.: 428,990

Related U.S. Application Data Continuation of Ser. No. 207,856, Dec. 14,1971, abandoned.

Foreign Application Priority Data Dec, 16, 1970 United Kingdom 59744/70U.S. Cl. 252/109; 252/121; 252/540;

252/557;252/D1G. 1 Int. Cl. CllD 9/10 Field of Search 252/117, 121, 109,538,

252/557, DIG. l, 540

Primary Examiner-Leland A. Sebastian Attorney, Agent, or Firm.lames J.Farrell, Esq.

[57] ABSTRACT The invention describes the use of salts of sulphonatedfatty acids as detergency builders. The use of C to C acids is requiredand a formulation containing 10 to 75% of a builder component includingat least one sulphonated fatty acid salt and 5 to 50% of a detergentactive is proposed. Preferred actives, which demonstrate increaseddetergency at specific ratios, are alkylaryl sulphonates, nonionicmaterials and alkane sulphonates.

7 Claims, 1 Drawing Figure DETERGENT COMPOSITIONS This is a continuationof application Ser. No. 207,856 filed Dec. 14, 1971, now abandoned.

This invention relates to detergent solid and liquid formulations. (Theformulations of the invention are particularly intended for the purposeof fabric washing.)

Detergent formulations contain an active ingredient and a buildermaterial together with other organic and inorganic substances havingspecific functions in the wash liquor. The builder material allows thedetergent active to perform its cleaning function efficiently. Phosphatematerials, for example sodium tripolyphosphate, have been used for manyyears as builder materials; however, recently concern has been expressedregarding the contribution of phosphate to the eutrophi cation of inlandwaters.

The present invention describes formulations containing a reduced or nillevel of phosphate which have good detergent properties and candemonstrate softening of fabric during washing.

The invention provides a detergent formulation comprising from to 75% byweight of a builder component consisting of water-soluble salt or saltsof an alpha-sulphonated saturated fatty acid or mixture thereofcontaining from 14 to 20 carbon atoms alone or in admixture with otherdetergency building materials, from 5 to 50% by weight of a detergentactive material, from 0.2 to 20% (preferably 0.2% to 15%) by weight ofalkali-metal salts of long-chain fatty acids, optionally 5 to 12% byweight of sodium silicate; the remainder being other known components ofdetergent formulations.

The preferred ranges within the broad definition of the invention arefrom to 50% by weight of the sulphonated fatty acid salts, from 15 to35% by weight of the detergent active material and from 5 to 15% ofalkali-metal salts of long-chain fatty acids.

The invention proposes the use of the monoor disalts (either single ormixed, for example sodium/potassium). At the pH value of the washliquors formed by the compositions of the invention the hydrogen ion ofa monosalt would also be ionised to form the doubly charged anion.

The sulphonated fatty acid salt will be used alone or as a mixture withone or more of the known detergency builders, for example so-calledprecipitant builders which form insoluble calcium salts, for examplesodium orthophosphate, and sodium alkyl and alkenyl succinates andmalonates, and also sequestrant builders which can be either organic orinorganic, for example sodium hydrofuran tetracarboxylate, sodiumpyrophosphate, sodium nitrilotriacetate, sodium ethylene diaminetetraacetate, sodium citrate, sodium tartrate, sodium malate, trisodiumcarboxymethyloxysuccinate, sodium oxydiacetate, sodium oxydisuccinate,and also polyelectrolyte builders such as sodium polyacrylate andcopolyethylene maleate. Both the sodium and potassium salts of thesulphonated fatty acid can be utilized although as will be appreciatedfrom the further description, the sodium salt is preferred. Theammonium, alkyl substituted ammonium and amine salts, for exampletriethanolamine (of use in liquid formulations) can be used. Theformulations will contain other known detergent formulation ingredientsselected from alkaline materials, e.g., silicate, sulphates, germicides,active oxygen carriers, e.g., perborates, persulphates,

2 percarbonates, antiredeposition agents, enzymes, fluorescers, perfumesand water.

The ingredient ranges quoted are broad because the inventioncontemplates that a formulation of this general formula can be used atcertain product concentrations depending on the country of use. Thus, inthe USA market detergent powders will usually be used at an in-useproduct concentration of 0.075 to 0.20% weight to volume, whereas in theEuropean type markets a product in-use concentration of 0.3% to 1%weight to volume is more usual. For the USA type markets theconcentration of sulphonated fatty acid salt will preferably be chosenin the higher part of the quoted range, i.e., 3575%, and for theEuropean type markets preferably in the lower range, i.e., l050%. Forthe USA market the surfactant concentration in the powder willpreferably be l050% and in the European type powders the surfactantconcentration will preferably be 525%. The use of a lower productconcentration in the USA requires that the formulation itself has ahigher concentration of active and builder material. It is advisable touse the products of the invention at a pH in the wash liquor of above9.5.

Examples of the anionic active used are alcohol sul phates (C andsulphonates, ether sulphates, olefin sulphonates, alkyl aryl sulphates,alkane sulphonates and cationic materials, for example quaternarynitrogen actives. Other anionic actives known for use in detergentformulations can be used. An example of the nonionic active used is theethoxylated alcohol class; the alcohol preferably having a chain lengthof C and an average ethoxylation of from 5 to 30, preferably 15 to 25.Other nonionics which will be usable are alkyl-phenols. Volume II ofSurface Active Agents and Detergents by Schwartz, Perry and Berch(lnterscience 1958) lists actives within these classes. Preferredactives are alkylbenzene sulphonates, nonionic materials, in particularethoxylated alcohols, and alkane sulphonates. The preferred ratios ofthese actives to the sulphonated fatty acid salt builder are:

Alkylbenzene sulphonate 2: more preferably to 5 Z more preferably 0 1:1

4 more preferably 1 2 Nonionic active 5 l l Alkane sulphonate l l Theactives olefin sulphonate, Dobanol 45 5 EO sulphonate and Tergitoll5-S-7 were shown to be comparable with an alkylbenzenesulphonate/sodium tripolyphosphate formulation.

The physical form of the solid formulations of this invention may be,for example, flakes, tablets, powders (e.g., blown or spray dried),granules and extruded forms.

The Applicants contemplate the use of synthetic fatty acids as well asnatural fatty acids for use in the sulphonated material. The preferredrange of sulphonated fully hardened fatty acid salt is from 10% to 40%.The Applicants have found that the alkyl radical must be at least C andpreferably C to give good building properties. This is not to say thatsome amount of C or lower cannot be tolerated, but such materials addlittle or nothing to the building efficiency. As natural fatty acids aremixtures of chain lengths it may be necessary to include some of thesenon-efficient materials in a formulation or undertake separation of thedesired chain lengths. The chain length of the sulphonated fatty acidsalt will be kept as low as possible because increase in chain lengthincreases the molecular weight and hence reduces the proportion of themolecule available for building properties. Further, the solubility ofthe salts falls with increase in molecular weight and it is believed thesodium salt would be of little value above a chain length of C TheApplicants have found that the C chain has the optimum buildingproperties and tallow fatty acid is the best practical source of fattyacid for sulphonation. The potassium salt is more soluble. To use thepotassium salt may require the other alkali-metal salts in theformulation to be substantially in the potassium form. The ammonium saltmay also be used and the triethanolamine salt is of particularapplicability to liquid formulations.

It is believed that alpha-sulphonated fatty acid salts achieve theirbuilding usefulness by precipitating the alkaline earth metal ions. Ithas been found that formulations according to the invention give fabricsoftening 4 Rw reflectance of washed material and applying the formula:

Alpha-sulphonated fatty acid salt 15 to 65% Alkyl benzene sulphonate 18%Alkaline silicate 10% Sodium sulphate approximately 12% Results ofspecific formulations (Examples 1 to 6) are given in Table l.

Table-l Detergency The higher numbers indicate better detergency.

Sodium tripolyphosphate (b) wash liquor at 60C. product concentration inwash 0.6% W/V Sodium fatty acid sulphonate Sodium tripolyphosphateproduct concentration 0.3% W/V.

in the wash and this effect is probably due to deposition of thisprecipitant on the fabric surface.

It is known that alpha-sulphonated fatty acid salts have detergentactive properties but appreciation of their properties as buildermaterials has provided the basis for the present invention.

Examples of formulations according to the invention will now be given.Formulations were prepared using the proportions given in the followingTable (by weight). It was found that the amount of lather obtainedgenerally increased with the amount of sulphonated fatty acid saltpresent. The soap (Pristerine 63 sold by Price Brothers of Bromborough,England) had a chain length distribution of C ,-2%; C -3 1%; C(saturated)-65% and C ,,(unsaturated)-2%. Soaps are alkali-metal saltsof long-chain (C -C fatty acids. The sulphonated acids were prepared byreacting the acid with sulphur trioxide.

Examples of the invention will now be given to illustrate, but notlimit, the invention.

The detergencies were measured using dacron/cotton test cloth soiledwith artificial sebum and vacuum cleaner dust in 18H water (Ca:Mg being2:1) with the aid of a Terg-O-Tometer (1H is 0.0001 M calcium). The washtemperature was 50 or 60C for 10 minutes followed by 1 minute rinse at25C.

The accompanying FIGURE has a graph which plots detergency (Y) againstseveral mixtures of actives (A) and sodium alpha-sulphonated fullyhardened tallow fatty acid (B).

The detergency (Y), quoted as a percentage, was determined using anElrepho reflectometer to measure the following parameters:

Rc reflectance of clean material Rs reflectance of soiled material Blownpowders were also tested, both with and with out enzymes, and containingan alkyl benzene sulphonate (Oronite 1060) as the surfactant, theseblown powders were found to be satisfactory.

In order to demonstrate the fabric softening effect, a formulationcontaining an alpha-sulphonated fatty acid salt (50%), alkylbenzenesulphonate (16%) was evaluated. A second formulation containing 20%alkylbenzene sulphonate was also tested and found satisfactory. Theclothes after washing in the procedure proposed earlier for thedetergency tests were tumble-dried and samples of clothes removed aftera specific number of washes and compared for softness with similarlyprepared samples washed using Standards A, B and C, the formulations forwhich are quoted below.

Standard Dodecyl benzene sulphonate Tallow alcohol sulphonate 0 Soap 0Sodium tripolyphosphate 40 Alkaline silicate 6 Sodium carbonate 0 Sodiumsulphate 30 Remainder being water, perfume N U1 ONOOOQQD 4 The betterfabric softening properties of the formulations of the invention will beappreciated.

Redeposition was also studied using various fabrics with Standards B andC quoted previously. The redeposition was measured as the loss ofreflectance after 25 wash cycles (see Table III) using an in-washproduct 6 The preferred ranges for the ratios of active to builder arefrom 1:6 to 6:1 and most preferred from 2:5 to 5:2.

Curve I in the FIGURE demonstrates the increase in concentration of0.15%. The product according to the 5 detergency achieved by theaddition of the sulphonated invention (D) contained 50% sodium fattyacid sulphofatty acid salt to the linear alkyl benzene sulphonate. nateand 20% alkylbenzene sulphonate as active.

Table 11 Fabric Softening sulphonated Product in Persons Number of fattyacid 7: Active Standard(s) use Number of in panel salt concentrationwashes panel selecting SFAS washed as softer 50 16 A 0.15% I l2 10 50 16A 0.15% 5 12 ll 50 16 A 0.15% 10 12 12 50 16 B 0.15% 1 12 12 50 16 B0.15% 5 12 12 50 16 B 0.15% 10 12 12 50 20 B and C 0.075% 1 24 21 50 20B and C 0.075% 5 24 23 50 20 B and C 0.075% 10 24 21 50 20 B and C 0.10%1 24 22 50 20 B and C 0.10% 5 24 23 50 20 B and C 0.10% 10 24 21 50 20 Band C 0.10% 24 22 50 B and C 0.15% l 24 23 50 20 B and C 0.15% 5 24 2450 20 B and C 0.15% 10 24 24 50 20 B and C 0.15% 15 24 24 50 20 B and C0.15% 25 24 23 Table 111 Redeposition EXAMPLE Reflectance loss of 25washes Example VII was repeated using a secondary C al- M, cohol 9 EO(Tergltol 15-S-9) as the (nonlonic) act1ve. xzz l The productconcentration was 0.1%. Dacron cotmfithick) 1 Dotted curve 11 in theFIGURE shows the detergengaprop cotton (thin) 523 i8? 3 cies achieved.Expressing the preferred ranges as perl'lm ene Terryptowemng 4A 39 42centages of the total we have Nylon 13.1 15.5 8.3

Nonionic active, 5 to 30% sulphonated fatty acid salt 40 to 65% ExampleVII A S ofd ter em wd The most preferred ranges are nonionic active 10to Linz r ilkyl iof betlzeneiiiigiigna'tl (H07, 20% together with 50 to60% of the sulphonated fatty Sodium alpha-sulphonated saturated fattyacid salt. It w1ll be apprec1ated that 1n a commercial ii g f gg z g35%) 45 formulation the total of active and builder will probably Sodiumsulphate, water 20% not equal 70% of the total composmon. The preferredranges for the ratios of active to builder are from 1:13 to 3:4, themost preferred being from 1:6 to 2:5. Curve were prepared, the total ofactive sulphonated fatty I1 demonstrates the increase in detergencyobtained by acid salt being always 70%. adding a salt of ana-sulphonated fatty acid to a non- Detergencies were determined using aTerg-O-Tomeionic active. ter at 90 rpm. The wash liquor was made up at0.15% product concentration in 18 hard water (CazMg EXAMPLE IX 2:1 Thewash was at 50C for 10 minutes followed by Example VII was repeatedusing a secondary alkane 1 minute rinse at 35C. The test cloth wasdacron/cotsulphonate (C to C chain length) as the active. The ton withvacuum cleaner dust as soil. product concentration was 0.1%. Dot/dashcurve 111 in The detergencies, measured as percentages are the FIGUREshows the detergencies achieved. Expressshown in continuous curve I inFIG. I. It will be seen ing the preferred ranges as percentages of thetotal we that preferred ranges are: have Detergent active 10 to 60%Alkane sulphonate active 5 to 50% sulphonated fatty acid salt 60 to 10%sulphonated fatty acid salt 20 to The most preferred ranges are from 20to 50% for the The most preferred ranges are alkane sulphonate ac- 65tive 10 to 35% together with sulphonated fatty acid salt active togetherwith 50 to 20% of the sulphonated fatty acid salt. It will beappreciated that in commercial formulations the total sum of activebuilder will normally not equal of the total.

35 to 60%. Expressed as ratios of active to builder the preferred rangesare from 1:13 to 5:2, the most preferred ratios being from 1:6 to 1:1.It will be noted that 7 addition of a salt of an alpha-sulphonated fattyacid increases the detergency of the active.

EXAMPLE X This Example demonstrates the criticality of chain length ofthe sulphonated fatty acid salt.

Linear alkyl (C ,)benzene sulphonate Sodium builder salt 50% Alkalinesilicate 57: Sodium sulphate. water 2571 was tested in a Terg-O-Tometerand the detergency measured as a percentage. The test cloth was dacron/cotton soiled with vacuum cleaner dust.

0.1% product concentration was used in 18 hard water (CazMg 2:1 with thepH at commencement adjusted to 9.5. The disodium salts of thea-sulphonated fatty acids listed below were compared as builders withsodium tripolyphosphate (STPP).

Fatty Acid Detergency (71) Stearic (C 44.7 Palmitic (C 37.2 Hardenedtallow (C 657:: C 3571) 38.l Palm (C t 50%: C 5071) 36.3 C 1 L3 STPP38.3

8 We claim: 1. A detergent formulation comprising i. from 10 to byweight of a builder component consisting of water soluble salt or saltsof an alphasulphonated saturated fatty acid or mixture thereofcontaining from 14 to 20 carbon atoms alone or in a mixture with otherdetergency building materials, from 5 to 50% by weight of a detergentactive material selected from the group consisting of an alkyl benzenesulphonate having from 8 to 20 carbon atoms and present in a ratio offrom 1:6 to 6:1 relative to the sulphonated fatty acid salt; anethoxylated alcohol wherein the alcohol has a chain length of C C and anaverage ethoxylation of from 5 to 30 present in a ratio of from 1:13 to3:4 relative to the sulphonated fatty acid salt; and an alkanesulphonate which is present in a ratio of from 1:13 to 5:2 relative tothe sulphonated fatty acid salt,

iii. from 0.2 to 20% by weight of an alkali metal salt of a long-chainfatty acid having from 10 to 20 carbon atoms or mixture thereof.

2. A detergent formulation according to claim 1 wherein the alkylbenzene sulphonate to sulphonated fatty acid salt ratio is from 2:5 to5:2.

3. A detergent formulation according to claim 1 wherein the ethoxylatedalcohol to sulphonated fatty acid salt ratio is from 1:6 to 2:5.

4. A detergent formulation according to claim 1 wherein the alkanesulphonate to sulphonated fatty acid salt ratio is from 1:6 to 1:1.

5. A detergent formulation according to claim 1, wherein the alkalimetal salts of long-chain fatty acids are present in an amount of from0.2 to 15% by weight.

6. A detergent formulation according to claim 1 including 5 to 12% of asodium silicate.

7. A detergent formulation according to any of claim 1, wherein thesulphonated fatty acid salt contains from 16 to 18 carbon atoms.

1. A DETERGENT FORMULATION CMPRISING I FROM 10 TO 75% BY WEIGHT OF ABUILDER COMPONENT ONSISTING OF WATER SOLUBLE SALT OR SALTS OF ANALPHA-SULPONATED SATURATED FATTY ACID OR MIXTURE THEREOF CONTAINING FROM14 TO 20 CARBON ATOMS ALONE OR IN A MIXTURE WITH OTHER DETERGENCYBUILDING MATERIALS, II. FROM 5 TO 50% BY WEIGHT OF A DETERGENT ACTIVEMATERIAL SELECTED FROM THE GROUP CONSISTING OF AN ALKYL BENZENESULPHONATE HAVING FROM 8 TO 20 CARBON ATOMS AND PERCENT IN A RATIO OFFROM 1.6 TO 6:1 RELATIVE TO THE SULPHONATED FATTY ACID SALT, ANETHOXYLATED ALOHOL WHEREIN THE ALCOHOL HAS A CHAIN LENGTH OF C 10-C20AND AN AVERAGE ETHOXYLATION OF FROM 5 TO 30 PRESENT IN A RATIO OF FROM1:13 TO 3:4 RELATIVE TO THE SULPHONATED FATTY ACID SALT AND AN ALKANESULPHONATE WHICH IS PRESENT IN A RATIO OF FROM 1:13 TO 5:2 RELATIVE TOTHE SULPHONATED FATTY ACID SALT, III FROM 0.2 TO 20% WEIGHT OF AN ALKALIMETAL SALT OF A LONG-CHAIN HAVING FROM 10 TI 20 CARBON ATOMS OR MIXTURETHEREOF.
 2. A detergent formulation according to claim 1 wherein thealkyl benzene sulphonate to sulphonated fatty acid salt ratio is from2:5 to 5:2.
 3. A detergent formulation according to claim 1 wherein theethoxylated alcohol to sulphonated fatty acid salt ratio is from 1:6 to2:5.
 4. A detergent formulation according to claim 1 wherein the alkanesulphonate to sulphonated fatty acid salt ratio is from 1: 6 to 1:1. 5.A detergent formulation according to claim 1, wherein the alkali metalsalts of long-chain fatty acids are present in an amount of from 0.2 to15% by weight.
 6. A detergent formulation according to claim 1 including5 to 12% of a sodium silicate.
 7. A detergent formulation according toany of claim 1, wherein the sulphonated fatty acid salt contains from 16to 18 carbon atoms.